Molded lignocellulosic material and method of making same



I I I Patented Apr. 9, 1940 MOLDED LIGNOCEILULOSIC MATERIAL AND METHOD OF MAKING SAME Arlie W. Schorgcrand John H. Ferguson, Madi- Ion, Wia, assignors to Burgess Cellulose Company, Freeport, 11].. a corporation of Delaware No Drawing.

This invention relates to a method for treatin natural lignocelluloses by a simple cooking and washing operationto produce a product which 4 upon drying may be hot-molded to produce. a I hard resinous material. The invention also relates to the products produced thereby.

It is an object of this invention to produce, by a simple and inexpensive process, a molding compound from natural lignocellulosic materials which may be hot-molded into a product possessing the desirable characteristics of products molded from the primary. material itself or admixed with artiflcial resins and the like.

Briefly, the process consists in cooking a natull ral lignocellulosic material with water within a limited range of pressures and for a. predetermined time to render water-soluble a part of the lignocellulosic material and particularly to dissolve .the hemi-celluloses. The residual product, after extraction of the water solubles and subsequent drying, contains a large part ofthe original thermoplastic resinous lignin, and may be hot-molded under pressure but without'the addition of a binder, into a hard resinous product 5 having a high strength and a high resistance to the absorption of water.

The raw material for the process is any natural lignocellulosic material such as wood, corn cobs, straw, bagasse, corn stalks, etc. When a 80 natural lignocellulosic material is referred to herein it includes manufactured productssuch as newsprint containing, for example, 70%-90% of coniferous ground wood. The ground wood therein is substantially in its original or natural 8 condition.

The lignocellulosic material, after being ground or otherwise comminuted, is cooked with water at an elevated pressure whereby part of the hemicelluloses are dissolved. The time, temperature, andpressure used during the cooking operation may vary within limits depending upon the speciflc properties-desired in the final product. .'Ihe cooking maybe done in water to which has been added small amounts of chemicals that function 45. as buffers whereby the pH of the cook is maintained within the range of- 4 to 6, and preferably between 4.5 to 5.5. The presence of moisture in Application April 1, 1937,

8 Claims. (CL 260-9) factors. If the water absorption-of the molded product is unimportant then cooking pressures (one hour cooking time) of from to 160 pounds (gauge reading) (148 C. to 188 C.) with hard wood sawdust give the best results. In a specific I instance a one hour cook at pounds (181 C.)

gave a product having its maximum strength when molded dry. When molded moist the maxi- This product which had been cooked 15 minutes when dry molded had substantially greater strength than that which was molded moist.

The water absorption and extent of flow of the molded product ppear to be more closely related to the cooking pressure than does its strength. Tests indicate that the maximum resistance to moisture is developed when the cooking pressure, using hardwood sawdust as the lignocellulosic material; is at about 180 to 200 pounds gauge pressure (193 C. to 198 0.), re-.

gardless of whether the cooking time is 15 min- I utes or one hour though these variables in themselves afiect the water absorption. For example, the moisture resistance of a moist-molded product decreases rapidly as the cookingpressure is decreased below 100 pounds gauge (170 C.) with a cooking time of one hour. If the same material is dry-m'olded the water resistance is subv stantially less and decreases rapidly at cooking pressures below pounds gauge (188 C.) The same material cooked for 15 minutes and moistmolded has an excellent water resistance when cooked at pressures above 160 pounds but atpressures somewhat below this disintegrates upon being immersed in waterfor several days. If

' dry-molded this product exhibits less water rethemolding compound during the molding operation aiiects appreciably the properties of the 50 molded product.

The cooking pressure and the cooking'time are closely related insofar as the strength of the molded product is concerned. The amount of moisture present and the hydrogen ion concen- 55 tration during the molding operation also are being the average for wood. Corn cobs lose 55 from 0.5% to 10%. About 5% gives excellent reabout 50% in weight on cooking at 160 pounds 'for 1 hour; newsprint loses about 23% under the same conditions, and straw about 44%.

A small amount of buffers, or active chemicals producing buifers, is added during the cook to neutralize the acetic acid split on from the wood. thereby keeping the hydrogen ion concentration at the desired point, usually about 5.5. For example, 2 of lime, Ca(OH) 2, may be added to the Wood before cooking. This lime forms an excellent buffer, calcium acetate, with the liberated acetic acid. This is a cheap and convenient method of forming the buffer in situ. If more than enough alkali or alkaline earth base is used than is necessary to neutralize the acid formed, the lignin may be attacked, thereby decreasing the amount of binder available in the molding compound. Ammonia also is a convenient alkali which may be added to the cook to neutralize the acetic acid liberated.

After the cooking operation is completed the cooked product is washed with water to'remove substantially all of the parts rendered watersoluble. The washing preferably is continued until the hydrogen ion concentration of the residue is such that its pH value is 5.5 to 7.0 as measured with the Truog soil indicator. In case of a low pH or prolonged time oi. molding, it is desirable to incorporate a bufi'er in the molding powder. The wet pulp, which is dark brown -in color, is then dried. The dried product called the primary material, is disintegrated in a mill to a powder which should pass through at least a 40- mesh screen and preferably a finer screen. The 65 mesh material gives excellent results. when powdered it is in a form for use as a molding compound either alone or in combination with, for example, other organic materials. The f primary material thus made consists of a filler and a binder. The filler is largely the unchanged cellulose of the lignocellulosic raw material. The

binder is primarily the substance resulting from the action of water on the lignin during .the cooking operation. Other fillers and binders may be added to the primary material.

This molding-powder is plastic and is well suited to molding operations. A small amount of moisture present in the powder is advantageous since the powder is rendered more plastic and the moisture resistance is increased as hereinbefore explained. The amount of moisture may vary sults. The primary product may be molded at a pressure of 1600 to 5000 pounds per square inch, a pressure of 3000 pounds being a favorable one, while it is maintained at an elevated temperature, usually above 100 C. A favorable temperature is 185 0., though temperatures of over 200 C. may be used. The molding time should be suflicient to produce the desired hard and resinous properties, 2 to 15 minutes usually suiflcing for small objects. The material is preferably molded by giving it a preliminary cold press in the mold at high pressure, 6000 to 7000 pounds per square inch, and then dropping the pressure. The mold is .then heated. As the product heats the pressure again rises. After being subjected to the desired pressure as hereinbei'ore specified for the necessary time, the mold may be cooled while maintaining some pressure. Hot or cold ejection is used.

The resultant product is hard, has a resinous appearance, remains thermoplastic and has many of the properties of products made by molding mixtures of a resin such as Bakelite and a filler Thus, 4

such as wood flour. The moisture absorption is very low, for example, less than 2% when a 2 inch disk which is inch thick is immersed in water for 18 hours. The modulus of rupture varies with the different materials. In a specific example it was 7000 pounds per square inch when molded with a small amount of water and 8400 pounds per square inch when molded dry. The density varied from 1.40 to 1.45. The best results are obtained if the hydrogen ion concentration of the primary product is controlled dur-- ing molding by the addition of a buffer such as sodium acetate.

A small amount of zinc stearate, for example, 1%, may be mixed with the molding-powder to secure better release in the mold. The zinc stearate acts as a lubricant and also aids the water resistance.

Phenols or aromatic amines may be incorporated with the primary product before molding to increase the water resistance, plasticity and strength of the molded product. A mixture of a phenol and an aromatic amine appears to be more desirable than an equal amount of either one alone since the plasticity and strength are increased. Phenols which may be used are phenol, nitrophenol, o-, m-, and p-cresol, alphaand beta-naphthol, catechol, pyrogallol, and paminophenol. Aromatic amines which may be used are aniline, o-, m-, and p-toluidine, alphaand beta-naphthylamine, p-toluolsulphonamide, phenyl ureas, phenyl guanidine. The amount of these phenols and aromatic amines which may be used varies over a wide range, usually about 1% to 10% of the weight oi. the primary product being desirable.

The primary product also is exceedingly useful as a filler to replace wood-flour and similar materials in the molding of plastics in which a resin is added in substantial'amounts, i. e. 20% to 80%. It is much more water-resistant than wood-flour and blends better with the resin, which may be either artificial or natural. The resultant molded product has improved waterresistance over that containing ordinary woodflour. The natural resins may be rosin and/or its salts and esters (ester gum), copal, shellac, sandarac, and damar. The artificial resins may be of the following types: phenol-formaldehyde, urea-formaldehyde, phthalic anhydride-glycerol (glyptals), cumarone, vinyl resins, cellulose nitrate, cellulose acetate, benzyl cellulose.

Following are specific examples which illustrate practical embodiments of our precess so that those skilled in the art may practice it. The time of molding given is for articles about 0.10 to 0.20 inch thick. The invention is not limited to these specific examples.

(1) One part of maple sawdust is cooked with 1 part or water in an autoclave at a pressure of 180 pounds per square inch (gauge) (193 C.) for one hour, the pH of the cook being kept at about 5.5 by the addition to the above mixture or 2%% (of the weight of the air dry sawdust) 0! calcium hydroxide. The cooked material is illtered in a filter press and washed with water until the pH is about 5.5 to 7.0. After the water solubles are substantially entirely removed the filter cake is dried at 110 0.. The dried material-is divided into three parts after disintegrating to a -mesh powder in a mill. (4) The first part is mixed with about 5% of water and 1% zinc stearate, introduced into a cold mold and pressed at 7000 pounds per square inch. The

pressure is then dropped to about zero and the mold is then heated to 185 C. The pressure in the mold is permitted to build up as a result of the temperature rise to 3000 pounds per square inch for 10 minutes. Cold ejection is used. (b) To the second portion of powdered primary product 2.0 per cent by weight or a mixture of equal parts of phenol and aniline is added and incorporated thoroughly therewith. This mixture is hot molded for 10 minutes at a pressure of 5000. pounds persquare inch and a temperature of (c) The third portion of powdered primary product is mixed with 6% of water and zinc stearate, introduced into a cold mold I and prepressed at 6000 pounds per square inch.

The pressure is dropped to 5000 pounds per squareinch and the mold heated to 170 C. for 10 minutes at this pressure after which it is cooled and the product ejected.

(2) One part of distintegrated corn cobs is cooked with 1 part of water at a pressure of 160 2 pounds (188 C.) for 1 hour in the presence of 5% sodium acetate as a buffer. The material is washed with water to a pH of 510 to 6.0 and after .substantially all of the water solubles are removed, is flltered and then dried to 5% moisture. After being distintegrated to pass through a 65- mesh screen it is molded for minutes .at a temperature of 185 C. and at'a pressure of 5000 poundsper square inch. v v

The pH as specified in each instance is that which is obtained with the Truog soil tester.

We claim:

1. In the process for producing a plastic moldable' product from a natural ligno-cellulosic material in which said material is cooked with water at a temperature of approximately 148 C. to 199 C. for approximately minutes to an hour to dissolve a part of the hemicelluloses and render said ligno-cellulosic material thermoplas-.

tic, said water containing an alkaline substance in amount sufficient to produce a pH of approximately 4.0 to 6.0 in the cooked mass at the end of the cook, leaching the cooked material with water until substantially all Qie water solubles are removed and drying theleached material. the step which comprises mixing with the dried material approximately 1% to 10% by weight of an aromatic amine.

2. The process of claim 1 in which the added material comprises aniline. I

3. A comminuted material plastic during hot .molding operations comprising a mixture or a ligno-cellulosic material and approximately 1% to 10%, based on the weight of the ligno-cellulosicmaterial of an aromatic amine, said lig-nocellulosic material being substantially free otthe water solubles produced in a natural ligno-v cellulosic material after pressure cooking with zinc stearate.

water for approximately 15 minutes to an hour at atem-perature of approximately 148 C. to 199 C. to render a part of the hemicelluloses water soluble, said comminuted material being capable of being hot pressed into a hard, resinous thermoplastic material and having a low moisture absorbing coefficient, said ligno-cellulosic material being the product resulting from cooking a natural ligno-cellulosic material with water at a temperature approximately 148C. to 199 C. for approximately 15 minutes to an hour in the presence of an alkaline substance suflicient in amount to produce a pH of approximately 4.0

to 6.0 in the cooked mass at the end of the cook, to render a part of the natural ligno-cellulosic material water soluble.

4. A hard, resinous product comprising a pressure hot molded mixture of a comminuted'plastic ligno-cellulosic material and approximately 1% to 10%, based on the weightof said ligno-cellulosic material, of an aromatic amine, said lignocellulosic material being substantially free of the water solubles contained in a natural lignocellulosic material after being cooked with water at a temperature of approximately 148 C. to 199 C. for approximately 15 minutes to an hour in the presence of an alkaline substance suflicient in amount to produce a pH of approximately 4.0.to 6.0 in the cooked mass at the end of the cook, said molded product being water resistant.

5. The product of claim 3 to which there has been added a small amount of finely divided 6. The product of claim 3 in which the lignocellulosic part of the comminuted molding ma-. terial has been'dried to a small moisture content.

7. In the process of producing a plastic, mold able, product from a natural ligno-cellulosic material in which said material is cooked with water at a temperature of approximately 148 C. to' 199 C. for approximately 15 minutes to an hour to dissolve a part of the hemicelluloses and render said ligno-cellulosic material thermoplastic, said water containing an alkaline substance in amounts suflicient to produce a. pH of approximately 4.0 to 6.0 in the cooked mass at the end of the cook, leaching the cooked material with water until substantially all the water solubles are removed and drying the leached material, the step which comprises mixing with the dried materialv approximately 1 percent to 10 percent by weight of a mixture of a phenol and an; aromatic amine.

8. The process of claim 7 in which the added material is a mixture of phenol and aniline.

ARLIE W. SCHORGER. JOHN H. FERGUSON. 

